Piezoelectric material and piezoelectric element

ABSTRACT

A piezoelectric element includes a first electrode, a piezoelectric film disposed on the first electrode, and a second electrode disposed on the piezoelectric film. The piezoelectric film is composed of piezoelectric material that is lead free and formed by mixing 100(1−x)% of material A having a spontaneous polarization of 0.5 C/m2 or greater at 25° C. and 100 x % of material B having piezoelectric characteristics and a dielectric constant of 1000 or greater at 25° C., wherein (1−x)Tc(A)+xTc(B)≧300° C., where Tc(A) is the Curie temperature of the material A and Tc(B) is the Curie temperature of the material B.

BACKGROUND

1. Technical Field

The present invention relates to piezoelectric materials that are usedfor piezoelectric elements.

2. Related Art

Piezoelectric elements possess a characteristic in which crystals arecharged when they are deformed, or they are deformed when they areplaced in an electric filed. As such, they are commonly used for liquidjet apparatuses such as ink jet printers.

Piezoelectric thin films such as PZT (lead titanate zirconate:Pb(Zr_(x)Ti_(1-x))O₃) films have been widely used for such piezoelectricelements.

Unfortunately, PZT films contain lead (Pb), and therefore could poseproblems for the safety of operators and the environment. Accordingly,research and development regarding lead free piezoelectric materials arebeing extensively conducted. For example, Japanese Laid-open PatentApplications JP-A-2004-6722, JP-A-2007-266346 and JP-A-2007-287745describe lead free piezoelectric materials.

Among the aforementioned piezoelectric elements, thin film piezoelectricelements in which a thin film piezoelectric layer is sandwiched betweenelectrodes have been studied and developed in recent years. Thin filmpiezoelectric elements are generally formed by a process in which apiezoelectric layer having a film thickness of several μm or less isformed on an electrode that is formed on a substrate, and an upperelectrode is formed on the piezoelectric layer. This process isconducted through micro-processing that is similar to a semiconductorprocess. Therefore, thin film piezoelectric elements have an advantagein that piezoelectric elements can be formed at a higher density thanordinary piezoelectric elements.

Although PZT is often used as the piezoelectric material for thin filmpiezoelectric elements, the use of lead free piezoelectric materials isnow also being considered.

In fact, the inventors of the present invention have been conductingresearch and development on piezoelectric materials, and examining theapplication of lead free piezoelectric materials and the improvement oflead free piezoelectric material characteristics.

BaTiO₃ and a variety of materials containing Bi may be representativeexamples of lead free piezoelectric materials. BaTiO₃ has a largepiezoelectric constant but has a low Curie temperature of about 120° C.,and thus has a problem with temperature stability. Many of the materialscontaining Bi have a high Curie temperature, but many of them havecertain problems, such as a small dielectric constant and a smallspontaneous polarization, as well as problems in temperature stabilitydue to the phase transfer temperature being lower than the Curietemperature. Thus, although lead free piezoelectric materials are beingwidely studied and developed as described above, in reality they haveboth advantages and disadvantages.

Other problems that may be encountered when using lead freepiezoelectric materials for thin film piezoelectric elements include acompositional shift due to the fallout of alkali metal elements inmaterials containing such alkali metal elements, and diffusion intolower electrode layers due to the high temperature crystallizationnecessary for BaTiO₃. In either case, it is difficult to use thesematerials for thin film piezoelectric elements.

BiFeO₃ has a high Curie temperature and a large spontaneouspolarization, and also has many other advantages suitable for thin filmformation. For example, BiFeO₃ does not have elements that would likelycause compositional shift, such as alkali metal elements, and has alower crystallization temperature, such that BiFeO₃ is attractingattention as a material for ferroelectric memories. Thus, attempts touse BiFeO₃ as piezoelectric material have also been made in recentyears. However, BiFeO₃ has a small dielectric constant, and thus cannotbe expected to achieve a high piezoelectric constant as a stand alonematerial.

In view of the foregoing, there has been a study to increase thepiezoelectric constant by mixing crystals of BiFeO₃ and BaTiO₃. However,when BaTiO₃ is mixed too much, BaTiO₃ becomes dominant and as a resultthe high Curie temperature and large spontaneous polarization of BiFeO₃cannot be best used. Also, if piezoelectric elements are manufacturedindependently with either of the materials, BiFeO₃ would likely resultin a poor dielectric property, and BaTiO₃ would deteriorate thepiezoelectric characteristics since it is difficult to make itscomposition uniform, and thus would likely form layers with a lowerdielectric constant. Therefore it is necessary to devise a solution forcontrolling the shortcomings of the respective materials, and to selectappropriate mixing ratios.

SUMMARY

In accordance with some aspects of the invention, it is possible toprovide BiFeO₃ and BaTiO₃ based piezoelectric materials that are leadfree and easy to prepare, yet still provide a large piezoelectricconstant and a high Curie temperature.

In accordance with an embodiment of the invention, a piezoelectricelement includes a first electrode, a piezoelectric film disposed on thefirst electrode, and a second electrode disposed on the piezoelectricfilm, wherein the piezoelectric film is composed of a piezoelectricmaterial that is lead free and a mixture of 100(1−x) % material A havinga spontaneous polarization of 0.5 C/m² or greater at 25° C., and 100 x %material B having piezoelectric characteristics and a dielectricconstant of 1000 or greater at 25° C., wherein (1−x)Tc(A)+xTc(B)≧300° C.where Tc(A) is the Curie temperature of the material A and Tc(B) is theCurie temperature of the material B.

According to the composition described above, the film performance canbe improved by the spontaneous polarization of the material A, and ahigh Curie temperature can be maintained. Furthermore, the piezoelectriccharacteristics can be improved by the material B.

In accordance with another embodiment of the invention, a piezoelectricelement includes a first electrode, a piezoelectric film disposed on thefirst electrode, and a second electrode disposed on the piezoelectricfilm, wherein the piezoelectric film is composed of mixed crystals ofBi(Fe, Mn)O₃ and Ba(Zr, Ti)O₃, expressed by a compositional formula of(1−x)Bi(Fe_(1-y)Mn_(y))O₃-xBa(Zr_(u)Ti_(1-u))O₃, where 0<x<0.40,0.01<y<0.10, and 0≦u<0.16.

According to the composition described above, the piezoelectriccharacteristics can be improved by Ba(Zr_(u)Ti_(1-u))O₃ whilemaintaining the spontaneous polarization and high Curie temperature ofBi(Fe_(1-y)Mn_(y))O₃. In this manner, when the composition is within therange described above, the mixed materials preferentially exhibit theirrespective characteristics that are useful as a piezoelectric material,whereby the film characteristics can be improved.

The first electrode or the second electrode may be formed from a singlelayer of metal or conductive oxide, or a laminate of layers of theaforementioned metal and conductive oxide. For example, the firstelectrode and the second electrode may be formed from any one of Pt, Ir,Au, Ti, Zr, Fe, Mn, Ni, Co, IrO₂, Nb:SrTiO₃, La:SrTiO₃, SrRuO₃, LaNiO₃,(La, Sr)FeO₃, and (La, Sr)CoO₃, or a laminate of layers of selected onesof the aforementioned materials. The aforementioned materials may beused for the first electrode or the second electrode.

The first electrode, the piezoelectric material film and the secondelectrode may be formed on a base substrate. For example, the basesubstrate may be formed from a semiconductor material, metal, ceramic orglass. Also, for example, the material composing the base substrate mayhave a melting point or a glass transition point of 650° C. or higher.Any of the aforementioned materials can be used for a base substrate onwhich piezoelectric elements are formed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a cross-sectional view showing a step of a method for forminga piezoelectric material in accordance with embodiment 1 of theinvention, and FIG. 1B is a table showing the pass and fail results ofthe hysteresis characteristics of samples No. 1-No. 9 whose compositionratios y are adjusted, respectively.

FIGS. 2A-2D are graphs showing the hysteresis characteristics of samplesNo. 2-No. 5.

FIGS. 3A-3D are graphs showing the hysteresis characteristics of samplesNo. 6-No. 9.

FIG. 4 is a table showing the pass and fail results of the hysteresischaracteristics of samples No. 10-No. 15 whose composition ratios x areadjusted, respectively.

FIGS. 6A-5D are graphs showing the hysteresis characteristics of samplesNo. 10-No. 13.

FIGS. 6A-6B are graphs showing the hysteresis characteristics of samplesNo. 14-No. 15.

FIG. 7 is a table showing the piezoelectric constant (d₃₃ [pm/V]) ofeach of samples No. 10-No. 12.

FIG. 8 is a table showing the pass and fail results of the hysteresischaracteristics of samples No. 16-No. 19 whose composition ratios u areadjusted, respectively.

FIGS. 9A-9D are graphs showing the hysteresis characteristics of samplesNo. 17-No. 19.

FIG. 10 is a table showing the piezoelectric constants (d₃₃[pm/V]) ofsamples No. 16-No. 19.

FIGS. 11A and 11B are graphs showing the relation between temperatures(° C.) and relative dielectric constants of samples No. 4-No. 8, and No.10-No. 12.

FIG. 12 is a graph showing the relation between temperatures (° C.) andsquared values of spontaneous polarization Ps of sample No. 12.

FIG. 13 is a table summarizing the heat resisting temperatures ofsamples No. 4-No. 8, and No. 11 and No. 12 and approximated values ofCurie temperatures.

FIG. 14 is a diagram showing the relation between the mixing ratiosbetween material A and material B and Curie temperatures.

FIGS. 15A-15C are cross-sectional views showing steps of a method formanufacturing an ink jet recording head (liquid jet head) having apiezoelectric element in accordance with a third embodiment of theinvention.

FIGS. 16A-16C are cross-sectional views showing steps of the method formanufacturing an ink jet recording head (liquid jet head) having apiezoelectric element in accordance with the third embodiment of theinvention.

FIGS. 17A-17C are cross-sectional views showing steps of the method formanufacturing an ink jet recording head (liquid jet head) having apiezoelectric element in accordance with the third embodiment of theinvention.

FIGS. 18A-18B are cross-sectional views showing steps of the method formanufacturing an ink jet recording head (liquid jet head) having apiezoelectric element in accordance with the third embodiment of theinvention.

FIG. 19 is an exploded perspective view of an ink jet recording head.

FIG. 20 is a schematic perspective view of part of an ink jet printerapparatus (a liquid jet apparatus).

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Preferred embodiments of the invention are described in detail belowwith reference to the accompanying drawings. It is noted that componentshaving the same function shall be appended with the same or relatingreference numbers and their description shall not be repeated.

Embodiment 1

FIG. 1A is a cross-sectional view showing a step of a method for formingpiezoelectric material in accordance with an embodiment of theinvention. First, as shown in FIG. 1A, a substrate 1, such as, forexample, a silicon (Si) substrate is prepared, and an elastic film(vibration plate) 2, such as, a silicon oxide film is formed on thesurface of the substrate 1. The silicon oxide film may be formed by, forexample, thermal oxidation to a film thickness of about 400 nm.

Then, on the elastic film 2, a TiAlN (titanium aluminum nitride) film 3is formed by, for example, a RF sputter method to a film thickness ofabout 100 nm. Next, an Ir (iridium) film 4 is formed by a DC sputtermethod on the TiAlN film 3 to a film thickness of about 100 nm, and thenan iridium oxide (IrO) film 5 is further formed thereon by a DC sputtermethod. The laminated films function as an adhesion layer between thesilicon oxide film and the lower electrode, or function as a diffusionprevention layer.

Next, a lower electrode 6 composed of a conductive film, such as, forexample, a platinum (Pt) film is formed on the iridium oxide film 5. ThePt film may be deposited by, for example, a DC sputter method to athickness of about 100 nm.

Then, a dielectric film (a dielectric film, a capacitance insulationfilm, a piezoelectric film) 9 is formed on the lower electrode 6. Thedielectric film 9 may be formed through coating a solution (sourcematerial solution) in which compounds (organometallic compounds) ofconstituent metals of Bi(Fe, Mn)O₃ and Ba(Zr, Ti)O₃ are dissolved in asolvent on the substrate by an appropriate coating method, such as, aspin coat method, and heat treating (drying, cleaning and sintering) thecoated film.

Embodiment Example 1

For example, a source material solution of Bi(Fe_(1-y)Mn_(y))O₃ adjustedto have an oxide concentration of 0.165 mol/kg is coated on a Pt film 6by a spin coat method at 1500 rpm, thereby forming a precursor film.Then, the film is heat treated at 350° C. for three minutes, therebydrying and cleaning the film. The cleaning is conducted to thermallydecompose organic compositions remaining in the precursor film into NO₂,CO₂, H₂O and the like, and to remove them. The coating, drying andcleaning steps are repeated ten times, and then sintering (heattreatment) is conducted at 650° C. for ten minutes by using a lampanneal furnace, thereby forming a Bi(Fe_(1-y)Mn_(y))O₃ film (the film 9)having a film thickness of about 400 nm. It is noted that the oxideconcentration means a concentration of Bi(Fe_(1-y)Mn_(y))O₃ that is anoxide in this case.

Then, on the Bi(Fe_(1-y)Mn_(y))O₃ film (9), a conductive film, such as,for example, a Pt film is deposited by a DC sputter method to athickness of about 100 nm to form an upper electrode 11, whereby astructure (a capacitor structure, a piezoelectric element structure) inwhich the Bi(Fe_(1-y)Mn_(y))O₃ film (9) is sandwiched by the upperelectrode 11 and the lower electrode 6 is formed.

Structures (see FIG. 1A) were formed with the conditions describedabove, using source material solutions of Bi(Fe_(1-y)Mn_(y))O₃ with thevalue y in a Bi(Fe_(1-y)Mn_(y))O₃ film (9) being adjusted in the rangebetween 0 and 0.1, and their dielectric characteristics were examined.

FIG. 1B is a table showing the pass and fail results of the hysteresischaracteristics of samples No. 1-No. 9 whose composition ratios y wereadjusted, respectively. FIGS. 2A-2D and FIGS. 3A-3D are graphs showingthe hysteresis characteristics of the samples. Amounts of polarization(μC/cm²) are plotted along the axis of ordinates, and voltage values (V)are plotted along the axis of abscesses. The hysteresis characteristicswere obtained by triangle waves at a frequency of 1 kHz.

As shown in FIG. 1B through FIG. 3D, it is clear that sample No. 1 withy=0 causes short-circuiting and therefore cannot be used as a dielectricfilm. Also, it is understood that sample No. 2 with y=0.01 and sampleNo. 9 with y=0.1 are leaky (have large current leak components) andtherefore cannot be used as dielectric films. Also, it is observed thatsample No. 7 with y=0.06 and sample No. 8 with y=0.07 tend to be leaky.On the other hand, the samples with y being in the range between 0.02and 0.05 obtained excellent hysteresis characteristic (dielectriccharacteristic).

Accordingly, it is understood that, as the content of Mn, the range of0.01<y<0.1 may be preferable, the range of 0.02≦y≦0.07 may be morepreferable, and the range of 0.02≦y≦0.05 may be even more preferable.

Embodiment Example 2

In this embodiment example, structures (see FIG. 1A) described abovewere formed by a process similar to that of Embodiment Example 1, usinga source material solution in which the value x in films of(1−x)Bi(Fe_(1-y)Mn_(y))O₃-xBa(Zr_(u)Ti_(1-u))O₃ was adjusted in therange between 0 and 0.5, and the dielectric characteristics of thestructures were examined. It is noted that the value y and the value uwere fixed at y=0.05 and u=0. In other words, mixed crystals of Bi(Fe,Mn)O₃ and Ba(Ti)O₃ were formed using a source material solution of(1−x)Bi(Fe_(0.95)Mn_(0.05))O₃-xBaTiO₃.

FIG. 4 is a table showing the pass and fail results of the hysteresischaracteristics of samples No. 10-No. 15 whose composition ratios x wereadjusted, respectively. FIGS. 6A-5D and FIGS. 6A-6B are graphs showingthe hysteresis characteristics of the samples, respectively. It is notedthat sample No. 10 is the same as sample No. 6.

As shown in FIG. 4 through FIG. 6B, it is clear that samples No. 14 andNo. 15 with x=0.4 and x=0.5, respectively, are leaky, and thereforecannot be used as dielectric films. Also, these samples exhibited lowerPm. Pm is polarization that is caused upon application of apredetermined voltage (in this example, 60V). Also, it was observed thatsample No. 13 with x=0.3 had a leaky tendency. On the other hand, whenthe value of x was in the range of 0-0.2, excellent hysteresischaracteristics (dielectric characteristics) could be obtained.

Accordingly, it is understood that, as the mixing ratio for (1−x)Bi(Fe,Mn)O₃ and xBa(Zr, 0Ti)O₃, the range of 0<x<0.4 may be preferable, therange of 0<x≦0.3 may be more preferable, and the range of 0<x≦0.2 may beeven more preferable.

Next, the piezoelectric characteristics of samples No. 10-No. 12 weremeasured. FIG. 7 is a table showing the piezoelectric constants(d₃₃/(pm/V)) of the respective samples. It is noted that thepiezoelectric constant (piezoelectric strain constant) d may beexpressed by a formula Si=dij×Ei, where S is the amount of strain and Eis an electric field. It is noted that i in the formula is the directionof strain, and j is the voltage application direction. The smaller thepiezoelectric constant d, the larger the strain of a piezoelectric film.It is noted that d₃₃ is a piezoelectric strain constant given, uponapplication of an electric field E3 in a direction, when a strain S3 isgenerated in a direction parallel with the foregoing direction. Forexample, d₃₁ is a piezoelectric strain constant given, upon applicationof an electric field E3, when a strain S1 is generated in a directionorthogonal to the foregoing direction. It is noted that the numbers “1,”“2” and “3” mean the x-axis direction, the y-axis direction and thez-axis direction, respectively. The piezoelectric constants d₃₃ weremeasured by using a double beam laser Doppler method.

As shown in FIG. 7, the piezoelectric constant improved when Ba(Ti)O₃was mixed (with x=0.1, x=0.2), than the case without mixingBa(Ti)O₃(x=0). Also, the piezoelectric constant was greater when themixing ratio was at x=0.2 than when it was at x=0.1.

Embodiment Example 3

In this embodiment example, structures (see FIG. 1A) described abovewere formed by a process similar to that of Embodiment Example 1, usinga source material solution of(1−x)Bi(Fe_(1-y)Mn_(y))O₃-xBa(Zr_(u)Ti_(1-u))O₃ in which the value u inthe films was adjusted in the range between 0 and 0.12, and thedielectric characteristics of the structures were examined. It is notedthat the value x and the value y were fixed at x=0.2 and y=0.05. Inother words, mixed crystals of Bi(Fe, Mn)O₃ and Ba(Zr, Ti)O₃ were formedusing a source material solution of 0.8 Bi(Fe_(0.95)Mn_(0.05))O₃−0.2Ba(Zr_(u)Ti_(1-u))O₃.

FIG. 8 is a table showing the pass and fail results of the hysteresischaracteristics of samples No. 16-No. 19 whose composition ratios u wereadjusted, respectively. FIGS. 9A-9D are graphs showing the hysteresischaracteristics of the samples, respectively. It is noted that sampleNo. 16 is the same as sample No. 12.

As shown in FIG. 8 through FIG. 9D, when the value u was in the range of0-0.12, excellent hysteresis characteristics (dielectriccharacteristics) were obtained. However, when u=0.12, Pm at 30V wasslightly lower than when u=0.08. Accordingly, it is observed that thedielectric characteristic reaches its peak when u is between 0.08 and0.12, and good hysteresis characteristics can be obtained up to aboutu=0.16. However, when Zr is increased with u being greater than 0.16,the Curie temperature of Ba(Zr, Ti)O₃ would lower, and the hysteresischaracteristic would deteriorate.

Therefore, it is understood that, as the content of Zr of(1−x)Bi(Fe_(1−y)Mn_(y))O₃-xBa(Zr_(u)Ti_(1-u))O₃, the range of 0≦u<0.16may be preferable, and the range of 0≦u≦0.12 may be more preferable.

Next, the piezoelectric characteristics of samples No. 17-No. 19 weremeasured. FIG. 10 is a table showing the piezoelectric constants(d₃₃/(pm/V)) of the respective samples. As shown in FIG. 10, when u isin the range between 0.04 and 0.12, good piezoelectric constants couldbe obtained. Also, when the content of Zr is increased in the rangebetween 0.04 and 0.12, there is a tendency that the piezoelectricconstant increases.

Embodiment Example 4

Next, to consider the Curie temperature of each of the samples, therelationship between the temperature (° C.) and the relative dielectricconstant of each of the samples were examined (see FIGS. 11A and 11B).

As shown in FIG. 11A, for samples No. 4-No. 8, there was a tendency thattheir relative dielectric constant increased with an increase in thetemperature, but an inflection point (Curie temperature) was notconfirmed. A similar tendency was also observed for samples No. 10-No.12, but an inflection point (Curie temperature) was not confirmed.Although a clear Curie temperature was not confirmed, the highesttemperature plotted, for example, for samples No. 11 and No. 12, inother words, the highest temperature (heat-resisting temperature) amongthe temperatures at which good hysteresis characteristic was obtainedwas 200-225° C., which proved that the samples had high heat resistingtemperatures. Moreover, samples No. 11 and No. 12 would exhibit a Curietemperature higher than at least the heat resisting temperaturedescribed above.

To further verify the Curie temperature, the relation betweentemperatures (° C.) and squared values (μC/cm²) of spontaneouspolarization Ps of sample No. 12 was examined (FIG. 12). In the graph,the x-intercept can be approximated as the Curie temperature, andtherefore the Curie temperature is observed to be about 320° C. In FIG.13, heat resisting temperatures of the respective samples andapproximated values of Curie temperatures are summarized. In view of theabove, it is understood that the samples have high Curie temperatures,and are therefore useful.

As described above in detail, by mixing (1−x)Bi(Fe_(1-y)Mn_(y))O₃ andxBa(Zr_(u)Ti_(1-u))O₃ in the ranges of 0<x<0.40, 0.01<y<0.10, and0≦u<0.16, and sintering the same, films having excellent dielectriccharacteristic and piezoelectric characteristic can be obtained. Also,their Curie temperatures can be improved, such that piezoelectricmaterials capable of enduring high-temperature use can be obtained.

In particular, by adjusting the range of the value x in the mannerdescribed above, it is possible to form piezoelectric materials having alarge piezoelectric constant and a high Curie temperature, and with noloss in the characteristics caused by a layer of low dielectric constantderived from Ba(Zr, Ti)O₃.

Moreover, by adding Mn while adjusting the value y in the mannerdescribed above, the dielectric property of the films can be improved,and therefore the film characteristics can be improved.

Furthermore, by adding (replacing with) Zr while adjusting the value uin the manner described above, a large piezoelectric constant caused bythe pinching effect can be obtained, and the Curie temperature can bemaintained at a sufficiently high temperature.

It is noted that the values x, y and u described above indicate mixingmol ratios of a solution (source material solution) in which compoundsof the respective elements (organometallic compounds) are dissolved in asolvent. When heat treatment is conducted at temperatures at which thevapor pressure of oxides of the respective element constituents issufficiently small, like the present embodiment example, compounds wouldbe formed with the mixing mole ratios described above. This phenomenonhas been confirmed by using ICP (high-frequency inductively coupledplasma) emission spectrometry.

Embodiment 2

Based on the consideration made in Embodiment 1, some design guidelinesto be applied at the time of forming lead free piezoelectric materialshall be examined. In other words, in the case of mixing two materials,the characteristics of materials and their mixing ratios shall beexamined.

First, as one material (ferroelectric material) A, a material having aspontaneous polarization of 0.5 C/m² or higher at 25° C. is selected. Asanother material B, a material having a relative dielectric constant of1000 or higher at 25° C. is selected.

When the Curie temperature of the material A is Tc(A), and the Curietemperature of the material B is Tc(B), the value x is selected toestablish a relation of (1−x)Tc(A)+xTc(B)≧300° C., and 100(1−x) %material A and 100 x % material B are mixed.

FIG. 14 is a graph showing the relation between Curie temperatures andmixing ratios between the material A and the material B. In other words,as shown in FIG. 14, when the material A and the material B become acomplete solid solution, the relation between the mixing ratio (1−x) andthe Curie temperature Tc may be approximated as a linear change fromTc(A) to Tc(B). Therefore, by selecting the mixing ratio in a manner tosatisfy the foregoing formula, it is believed that materials having ahigh Curie temperature can be obtained while making the best use of thecharacteristic of each of the materials mixed.

Embodiment 3

A method for manufacturing a piezoelectric element that uses thepiezoelectric material with excellent characteristics examined above inembodiments 1 and 2 is now described. FIGS. 15A-18B are cross-sectionalviews showing steps of a method for manufacturing an ink jet recordinghead (liquid jet head) having the piezoelectric element in accordancewith the present embodiment. FIG. 19 is an exploded perspective view ofthe ink jet recording head. FIG. 20 is a schematic perspective view ofpart of an ink jet printer (a liquid jet apparatus).

With reference to FIGS. 15A-20, a method for manufacturing piezoelectricelements and the like, and their structures shall be described.

First, as shown in FIG. 16A, a substrate (base substrate) 1, such as,for example, a silicon (Si) substrate is prepared, and a silicon oxidefilm as an elastic film (vibration plate) 2 is formed on the surface ofthe silicon substrate 1. The silicon oxide film 2 may be formed by, forexample, thermal oxidation.

Then, as shown in FIG. 15B, a laminate film of TiAlN film/Irfilm/iridium oxide film as described above, is formed on the elasticfilm 2. In this example, the laminate film is indicated by a referencenumeral 4A.

Next, a lower electrode 6 composed of a conductive film, such as, forexample, a platinum (Pt) film or the like is formed on the laminate film4A. The Pt film may be deposited by, for example, a DC sputter method.Then, the lower electrode 6 is patterned (see FIG. 15C).

Next, as shown in FIG. 16A, a piezoelectric film (a piezoelectric body,a piezoelectric layer) 9 is formed on the lower electrode 6. Morespecifically, a source material solution with the values x, y and uadjusted as described above in embodiment 1 is coated on the substrateby an appropriate coating method, such as, a spin coat method, and thenthe film is heat treated (for drying, cleaning and sintering), therebyforming a piezoelectric film 9. As the material for the piezoelectricfilm 9, the materials described above in embodiment 2 may be used.

Next, as shown in FIG. 16B, a conductive film (11), such as, forexample, a Pt film is deposited on the piezoelectric film 9 by a sputtermethod. Then, as shown in FIG. 16C, by patterning the conductive film ina desired shape, an upper electrode 11 is formed. In this instance, thepiezoelectric film 9 below the conductive film may be patterned at thesame time. As a result, a piezoelectric element PE made of a laminate ofthe lower electrode 6, the piezoelectric film 9 and the upper electrode11 is formed.

It is noted that, as the lower electrode 6 and the upper electrode 11, asingle element of metal or conductive oxide, or a laminate of layers ofthe foregoing materials can be used. More specifically, any one of Pt,Ir, Au, Ti, Zr, Fe, Mn, Ni, Co, IrO₂, Nb:SrTiO₃, La:SrTiO₃, SrRuO₃,LaNiO₃, (La, Sr)FeO₃, and (La, Sr)CoO₃, or a laminate of layers ofselected ones of the aforementioned materials may be used. The metalsamong the above representative materials can suppress mutual diffusionwith the piezoelectric material, or can suppress deterioration of thecharacteristics that may be caused by mutual diffusion to a minimum, asthe metal is one of the constituents of the piezoelectric material.Also, the conductive oxides among the above representative materialshave the same crystal structure as that of the piezoelectric material,and therefore can form cleaner electrode/piezoelectric interfaces at thetime of crystal growth.

Next, as shown in FIG. 17A, a conductive film, such as, for example, agold (Au) film is deposited on the piezoelectric element PE (on theupper electrode 11) by a sputter method, and patterned in a desiredshape, thereby forming a lead electrode 13.

Then, as shown in FIG. 17B, a protective substrate 15 is mounted on andbonded to the piezoelectric element PE (on the substrate 1). Theprotective substrate 15 has a recessed section 15 a in alocation/portion corresponding to the piezoelectric element PE, and alsohas opening sections 15 b and 15 c.

Then, as shown in FIG. 17C, the back surface of the substrate 1 (thesurface on the opposite side of the surface thereof where thepiezoelectric element PE is formed) is polished, and further etched bywet etching, thereby reducing the film thickness of the substrate 1.

Then, as shown in FIG. 18A, as a mask film 17, for example, a siliconnitride film is deposited on the back surface of the substrate 1, and ispatterned in a desired shape. Then, the substrate 1 is anisotropicallyetched, using the mask film 17 as a mask, thereby forming an openingsection 19 in the substrate 1. The opening section 19 may be formed fromopening regions 19 a, 19 b and 19 c. Then, an outer circumferential areaof the substrate 1 and the protective substrate 15 is removed andreshaped by dicing or the like.

Next, as shown in FIG. 18B, a nozzle plate 21 having a nozzle aperture(nozzle opening) 21 a at a position corresponding to the opening region19 a is bonded to the back surface of the substrate 1. Also, acompliance substrate 23 to be described below is bonded to the upperportion of the protective substrate 15, and appropriately divided(scribed). By the steps described above, an ink jet recording headhaving a plurality of piezoelectric elements PE is substantiallycompleted.

It is noted that, as the material for the substrate 1, other materials,such as, semiconductor material other than Si, metal, ceramics, andglass may be used. Also, even when the material composing the substrate1 has a melting point or a glass transition point, such material canendure high-temperature uses if the melting point or the glasstransition point is higher than 650° C.

By using any of the materials described above in the embodiments 1 and 2as the material for the piezoelectric film 9 in this manner, thecharacteristics of the piezoelectric element can be improved. Inparticular, as the materials are lead free, environmentally consciousproduct manufacturing can be conducted.

Also, lead free piezoelectric materials, which are material systemsincluding alkali metal elements, may entail problems, such as,compositional shifts due to fallout of alkali metal elements, anddiffusion into a lower electrode due to the heat at the time ofcrystallization. However, in addition to a high Curie temperature and alarge spontaneous polarization, the materials in accordance with theembodiment described above do not contain elements, such as alkali metalelements, which would likely cause compositional shifts, and also havemany more advantages, such as low crystallization temperature, such thatthe materials in accordance with the embodiment described above can befavorably used for piezoelectric elements.

Moreover, the compositions of the materials described above can bereadily adjusted by solution processing, and the materials describedabove can be readily accommodated for pattern miniaturization.Accordingly, the materials in accordance with the present embodimentdescribed above can be readily accommodated for miniaturization andhigher resolution of heads and printers to be described below.

FIG. 19 is an exploded perspective view of an ink jet recording head,and sections thereof corresponding to those shown in FIGS. 15A-18B shallbe appended with the same reference numbers.

As shown in the figure, each opening region 19 a located below eachpiezoelectric element PE defines a pressure generation chamber. When anelastic film 2 is driven by the piezoelectric element PE and displaced,ink is ejected from a nozzle aperture 21 a. In this embodiment, thecombination of the piezoelectric element PE and the elastic film 2 isreferred to as an actuator device. It is noted that FIG. 19 merely showsan example of the structure of an ink jet recording head, and it is tobe understood that many appropriate changes can be made to the structurethereof, such as, the shape of each of the piezoelectric elements PE,their arrangement direction, and the like.

FIG. 20 is a schematic perspective view of part of an ink jet printerapparatus (a liquid jet apparatus) 104. As shown in the figure, the inkjet recording heads described above are assembled in jet head units 101Aand 101B. Also, cartridges 102A and 102B composing ink supply devicesare detachably mounted on the jet head units 101A and 101B,respectively.

Also, the jet head units 101A and 101 b are mounted on a carriage 103,and attached to an apparatus main body 104. The carriage 103 is moveablydisposed with respect to the axial direction of a carriage shaft 105.

The driving force of a driving motor 106 is transmitted to the carriage103 through a timing belt 107, whereby the jet head unites 101A and 101Bmove along the carriage shaft 105. Also, the apparatus 104 is providedwith a platen 108 along the carriage shaft 105, such that a recordingsheet (for example, a sheet of paper) S is transferred onto the platen108. Ink is discharged from the jet head units 101A and 101B and printedon the recording sheet S.

It is noted that, in the embodiment described above, the ink jetrecording head is described as an example. However, the invention iswidely applicable to liquid jet heads, and can be used for, for example,a color material ejection head that is used for manufacturing colorfilters for liquid crystal displays, a liquid ejection head that is usedfor ejecting liquid electrode material for organic EL displays, EFDs(field emission displays) and the like, and a bioorganic material jethead used for manufacturing bio-chips.

It is noted that, in the embodiment described above, the ink jetrecording head having piezoelectric elements is described as an example.However, the piezoelectric elements in accordance with the embodimentare widely applicable to ultrasonic devices such as ultrasonicoscillators, pressure sensors and the like, without being limited tothose used in ink jet recording heads.

It is noted that the embodiment examples and application examplesdescribed above in accordance with the embodiments may be appropriatelycombined, or changed or improved depending on their use, and theinvention shall not be limited to the embodiments described above. It isto be understood that embodiments according to such combinations, ormodifications or improvements can be included in the scope of theinvention.

This application claims priority to Japanese Patent Application No.2008-095054 filed Apr. 1, 2008 which is hereby expressly incorporated byreference herein in its entirety.

1. A piezoelectric element, comprising: a plurality of electrodes; and apiezoelectric material which includes Bi, Fe, Mn, Ba and Ti, wherein aCurie temperature of the piezoelectric material is 200° C. or more. 2.The piezoelectric element according to claim 1, wherein thepiezoelectric material consists of a mixed crystal including Bi(Fe,Mn)O₃ and BaTiO₃.
 3. The piezoelectric element according to claim 2,wherein Bi(Fe, Mn)O₃ is expressed by a compositional formula ofBi(Fe_(1-y), Mn_(y))O₃ and 0.01<y<0.1.
 4. The piezoelectric elementaccording to claim 2, wherein Bi(Fe, Mn)O₃ is expressed by acompositional formula of Bi(Fe_(1-y), Mn_(y))O₃ and 0.02<y<0.07.
 5. Thepiezoelectric element according to claim 2, wherein the piezoelectricmaterial is expressed by a compositional formula of (1−x)Bi(Fe,Mn)O_(3-x)BaTiO₃ and 0<x<0.4.
 6. The piezoelectric element according toclaim 2, wherein the piezoelectric material is expressed by acompositional formula of (1−x)Bi(Fe, Mn)O_(3-x)BaTiO₃ and 0<x<0.3. 7.The piezoelectric element according to claim 2, wherein thepiezoelectric material is expressed by a compositional formula of(1−x)Bi(Fe, Mn)O_(3-x)BaTiO₃ and 0<x<0.2.
 8. The piezoelectric elementaccording to claim 1, wherein the piezoelectric material furtherincludes zirconium (Zr).
 9. The piezoelectric element according to claim1, wherein at least one of the electrodes is platinum.
 10. A liquidejection head, comprising the piezoelectric element according toclaim
 1. 11. An ink jet printer, comprising the liquid ejection headaccording to claim 10.